1-Alkenylthis and chloroalkylthia-carbonyl)-octahydroindoles

ABSTRACT

Substituted azabicycloalkanes of the formula I   wherein R represents an alkyl radical which contains 2 or 3 carbon atoms and is substituted by chlorine or a straight-chain or branched alkenyl radical containing 3 or 4 carbon atoms, R1 and R2 represent hydrogen or the one represents methyl and the other represents hydrogen, and n is the number 1 or 2, may be used for influencing the growth of plants, preferably for combating weeds in rice-cultures.

United States Patent [19] Storm et al.

July 1975 1l-ALKENYLTHIS AND CHLOROALKYLTHIA-CARBONYL OCTAHYDROINDOLESlnventors: Elmar Sturm, Arlesheim; Hans Joerg Cellarius, Riehen;Christian Vogel, Binningen, all of Switzerland Assignee: Ciba-GeigyCorporation, Ardsley,

Filed: Sept. 10, 1973 Appl. No.: 395,884

Related U.S. Application Data Division of Ser. No. 216,778, Jan. 10,1972, Pat. No. 3,776,912.

Foreign Application Priority Data Jan. 14, 1971 Switzerland 553/71 U.S.Cl 260/326.12 R

C07d 27/56 Field of Search 260/326.12 R

References Cited UNITED STATES PATENTS 3/1973 Richter et al. 260/326.12R X Primary Examiner-Joseph A. Narcavage Attorney, Agent, orFirmFrederick H. Rabin ABSTRACT Substituted azabicycloalkanes of theformula I 2 "Claims, No Drawings ll-ALKENYLTHTS ANDCll-llLRUALKYLTHllA-EARBNYL)- UQTAHYDRUHNDQLES This is a division ofapplication Ser. No. 216,778, filed on Jan. 10, 1972, now US. Pat. No.3,776,912.

The present invention relates to substituted azabicycloalkanes, processfor their manufacture, also to selective herbicidal agents which containsuch substituted azabicycloalkanes as active substances, and toprocesses for combating grass-like weeds wherein the new activesubstances are used or the agents that contain them.

The term azabicycloalkanes is used here and hereinafter to denotesubstituted 2-azabicyclo[4.4.0]- decanes (decahydroquinolines) and 7-azabicyclo[4.3.01-nonanes (octahydroindoles).

The substituted azabicycloalkanes according to the invention correspondto the formula I:

wherein R represents an alkyl radical which contains 2 or 3 carbon atomsand is substituted by chlorine or a straight-chain or branched alltenylradical containing 3 or 4 carbon atoms, R, and R each represent hydrogenor the one represents methyl and the other represents hydrogen, and n isthe number 1 or 2.

By an alkyl radical which contains 2 to 3 carbon atoms and issubstituted by chlorine is to be understood the mono-substituted ethyl,n-propyl or isopropyl radical.

The straight-chain or branched alkenyl radicals containing 3 to 4 carbonatoms include the allyl, Z-butenyl, 3-butenyl and the methylallylradical.

The substituted azabicycloalkanes of the formula I are obtainedaccording to the invention by reacting an azabicycloalkane of theformula ll i er: 13. (11) T i R, 11

either with a thiocarbonic acid halide of the formula III (Ill) or withthe constituent components of such a thiocarbonic acid halide, namelyphosgene and an alkali metal salt of a mercaptan of the formula IV R SHin the presence of an acid binding agent. in the formulae ll to ll'V, R,R R and n have the meanings assigned to them under formula I and Hal inthe formula ill represents chlorine or bromine. it is advisable to carryout the reactions in a solvent or diluent which is inert towards thereaction components. The nature of the sol vent to be used is verylargely determined by the acid binding agent used in the reaction. Iforganic bases, such as tertiary amines, are used, it is advisable to useorganic solvents also. in the case of inorganic bases, water and aqueousmixtures of organic solvents which are miscible with water are suitable.in general, the following tertiary amines may be used as acid bindingagents: pyridine and pyridine bases, triethylamine etc. The respectiveazabicycloalltane of the formula ll, used in excess in the reaction, maylikewise be used as acid binding agent. Suitable inorganic bases are thehydroxides and carbonates of alkali and alkaline earth metals, chieflysodium hydroxide, sodium carbonate, potassium carbonate, also thehydroxides and carbonates of lithium, barium, strontium, magnesium, aswell as quaternary ammonium compounds which react as bases in thepresence of water, for example tetramethylammonium hydroxide etc.

As solvents there may be used: aliphatic and aromatic hydrocarbons andhalogenated hydrocarbons, such as benzene, toluene, xylenes, petroleumether, chlorobenzene, methylene chloride, chloroform, carbontetrachloride, ether and ether-like solvents such as dialltyl ether,tetrahydrofuran. Suitable solvents which are miscible with water arealkanols, ltetones etc.

in the reaction of an azabicycloaikane of the formula ii with phosgeneand an alkali metal salt of a mercaptan of the formula i theazabicycloalkane-Z-carboxylic acid halide obtained as intermediateproduct can be reacted without further purification with the salt of themercaptan.

According to a further process of the present invention the newsubstituted azabicycloalkanes of the formula H are obtained by reactingan azabicycloalkane of the formula ii, in the presence of an acidbinding agent, with carbon oxysulfide and subsequently with achloroalltylating agent or an alkenylating agent. Suitable acid bindingreagents are those cited above, preferably the alkali metal hydroxides.Suitable chloroalkylating agents are primarily chloroalltyl halides.

The reactions according to the invention of a substitutedazabicycloalltane of the formula ll according to one of the indicatedmethods to give compounds of the formula i are carried out attemperatures of C to +l0OC, preferably between 0C and +C.

Some of the azabicycloalkanes of the formula H are known and some arenew compounds. The new compounds are manufactured in known manner byhydrogenatirig the corresponding aromatic heterocycles at lOOl80C and100-200 gauge pressure, in aqueous emulsion and in the presence of noblemetal catalysts, for example ruthenium/carbon catalysts.

The starting compounds comprised by the formula H are present in 2isomeric forms: in the cisand in the transconfiguration. in the case ofthe 2- azabicyclo[4-.4.0l-decane (decahydroquinoline), with R and Rrepresenting hydrogen in the formula ll, the cisand trans-isomers areeasily isolated and lead to 2 series of compounds of the formula i withcisand trans-configuration The new substitutedazabicycloalkanes of theformula I possess excellen'tiherbicidal properties and are suitablepartly as'general herbicides and partly for combating weeds andgrass-like weeds in rice cultures (water anddry rice cultures).Varieties of weeds which are difficult to combat in rice cultures areattacked and destroyed by the compounds of the formula 1. Examples ofsuch weeds in water rice cultures are: Echinochloa sp., Eleocharis sp.,Monochoria, Sagittaria, Panicum sp.=', Cyperaceen, Rotala, Lindernia,Vandellia, Paspalum sp., etc.; and in dry rice cultures likewiseEchinochloa sp., Digitaria sp., Brachiaria sp., Sida sp., Cyperaceen,Acanthosperum sp. etc. Since the active substances gradually destroy theundesirable plants and thus do not have any excessively deleteriouseffect on the oxygen balanceand on the balance of nature, they are very{well suited for application in water rice cultures. Moreover, theactive substances possess a broad activity spectrum against variouswater weeds, for example against emersed plants, aquatic plants with andwithout floating leaves, submersed plants, algae etc. Both the cis andthe trans-azabicycloalkanes of the formula I as well as mixtures of bothformsare herbicidally active.

The broad activity spectrum of the new substituted azabicycloalkanes ofthe formula I also makes it possible to use them in the important taskof combating weeds and grass-like weeds in the area surrounding the ricecultures, for example ditches, canal beds, dams etc. Not only the citedgrass-like weeds occu'rring'in ricc cultures but also other grass-likeand broad-leaved weeds are destroyed by these active substances. The

active substances may be used for destroying a crop of weeds which hasalready sprouted when preparing the rice beds and after the crop plantshave emerged. Both rice which is planted in water and that which isplanted dry do not suffer any damage when the new substitutedazabicycloalkanes are applied in the conventional concentrations anddamage which is very largely reversible when high rates of applicationare used. The rates of application vary and depend on the time ofapplication; they are between 0.5 and 6 kg of active substance perhectare, preferably 4 kg per hectare, in the case of application beforethe plants have germinated Rates of application of 10-30 kg of activesubstance per hectare are used to totally destroy the entire crops ofweeds, for example on the fallow land neighbouring on the cultivatedareas and to determine the general herbicidal activity. The croprotation important for the rice culture may proceed on application ofthe new active substances without any detrimental effects.

The azabicycloalkanes of the formula I may also be used furthermore asgrowth regulators, for example for defoliating, delaying blossoming etc.The new compounds influence the vegetative plant growth and germinationpower and promote fruit development and the evolution of abscissiontissues. The development of side shoots in various species of plants isvery substantially diminished. The new compounds also have a promotoraction, for example the latex flow in l-levea brasiliensis is promoted.As experiments have shown, the rooting of seedlings and cuttings andalso the tuber formation in potatoes are favourably influenced. Thegermination power of seeds, for example of seed potatoes and legumes, ispromoted on the use of low and prevented on the use of highconcentrations.

' Both effects are of economic importance. In the case of manyornamental and useful plants it is-possible to control the term ofblossoming and the number of blossoms. If all shurbs blossomsimultaneously. they can be harvested within a comparatively short time.

Experiments also showed that a thinning out of blossom and fruitoccurred in fruit trees. Furthermore, the ripening and colouring offruit, for example in the case of apples, peaches, tomatoes, bananas andpineapples, were accelerated and improved. The abscission of fruit andleaves is greatly facilitated by the formation of abscission tissue afactor which is of great economic importance in the mechanicalharvesting of, for example,".

citrus fruit or cotton. 1

Substituted azabicycloalkanes of the formula I have hitherto not beendescribed Herbicidal azabicyclo- [3.2.2]-nonanes andpolymethyleneiminothiocarbamates are described in U.S. Pat. No.s3.344.134 and 3.198.786 respectively, but their action on grass-likeweeds with good selectivity in rice is slight and dicotyledonous weedsare not damaged. With comparable selectivity towards rice, the activesubstances according to the invention of the formula I have a muchbetter action against grass-like weeds and a broad activity spectrumtowards dicotyledonous weeds. Even when used in very low rates ofapplication, some are herbicidally active against numerous grass-likeweeds against which the cited comparative compounds show no activity,and they are well tolerated by cereals, especially maize and wheat, alsosoya and cotton.

The herbicidal agents are manufactured by mixing the active substanceswith suitable carriers and/or dis-' persing agents. In order to broadenthe activity spec'- trum it is possible to add to these agents stillother herbicides, for example from the series of the triazines, such ashalogeno-diamino-s-triazines, alkoxyand alkylthio-diamino-s-triazines,triazoles, diazines, such as uraciles, aliphatic carboxylic acids andhalogenocarboxylic acids, halogenated benzoic'acids and phenylaceticacids, aryloxyalkanecarboxylic acids, hydrazides, amides, nitriles,esters of suc'hcarboxylic acids,

carbamic acids and thiocarbamic acids, phenyl ureas etc.

The following Examples illustrate the process for the manufacture of theazabicycloalkane derivatives of the formula 1.

EXAMPLE 1 vpercent of theory) ofl-(allylthiocarbonyl)-transdecahydroquinoline (b.p. '1lO-ll6C/0.2 Torr).

EXAMPLE 2 Beneath a solution of 13.9 g of cis-decahydroquinoline in 200ml of diethyl ether is introduced a layer consisting of an aqueoussolution of 4 g of sodium hydroxide. While stirring vigorously andcooling to 05C, 9.8 g of phosgene is passed into this mixture.

5 6 When the mixture shows a neutral reaction, the ether (j i d phase isSeparated and added dropwise to a suspension 8 I b t H b 139 1400/ 15 Tu a of 13 g of sod1um-(3-chloro-propyl)-mercapt1de 1n abdfgguin liiieony as on solute ether. The batch is left to stand for 24 hours and t 9l-(2-chloroethylthio-carbonyl)-8- l50-l52/O.l Torr then the resultingpreclpltate is collected by suction til methybdecahydmquincline tratlon.The ether is evaporated off and the resldual Oll so obtained isdistilled in vacuo to yield 19 g (68 per- 10 l'(3'mchlol'opmPylthmcar'1424457009 bonyl)-octahydro1ndole cent of theory) ofl-(3-n-chloro-propylthiocarbonyl)- cis-decahydroquinoline (b.p.140-142C/0.01 Torr). "y 9- y Torr octahydromdole l0 1 EXAMPLE 3 12l-(3-n-chloropropylthio- 145-150/0.1 Torr To a suspension of 13.9 g oftransdecahydroquinoline in 200 ml of water are added 4.0 g of sodiumhydroxide and, while stirring slowly, 8.0 g 01' rbon ox l hi e a e sedint e ixt a ysu p d r pas 0 th m ure t 15 The herblcldal actlon of thenew compounds is illus- O -5 C over the course of 1 hour. After afurther quartrated by the followlng tests. ter of an hour 23 g ofl,3-bromochloropropane are 1 added all at once and the batch is stirredfor hours Selective Pre-emergence Test with sown Test Plants at 20C. Theprecipitated oil is taken up in ether, the ether solution shaken outwith dilute hydrochloric acid, 20 Immediately after sowing the testplants in seed washed with water, dried and evaporated in vacuo. Thedishfis the active Substances, 1n the form Of an q u resulting oil isdistilled in vacuo. 10.6 Grams (38 per- SUSPCIISIOII (Obtained ffOm a 25Percent Wettable P cent of theory) of l-(3-n-chloropropylthiocarbonyl)-der), are applied to the surface of the SOll. The seed O Otrans-decahydroqulnolme are obtalned 1n the form of dlshes are p y'l P Cand 50*7O a colorless oil (b.p. 130-138C/0.01 Torr). 25 Pelicantrelatlve atmospherlc humldlty The compounds of h formula I hsted Table 1l Evaluation takes place 28 days according to the folmanufacturedaccording to the methods described in lowing key: these Examples byusing corresponding amounts of azabicycloalkane and thiocarbonic acidhalide of the f r ula 111 or carbon ox sul hide and alk latin or 30 O my p y g 9 plants undamaged =control alkenylatmg) agent. I plants diedOff 8-2 intermediate stages of damage TABLE 1 The following test plantswere sown:

11:11:. Compound Bolling Point rice y) yz rice (in water) 0 Wheat(Trilicum vulgare) 4 l-(allylthio-carbpnyl)-c|s- 106-1 10 /0.05 TorrSoya (Glycine hispida) decahydroqumo me cotton (Gossypium) a maize (Zeamais) 5 l-(allylthio-carbonyl)-2-methyl- 123-124 [0.01 Torr ray grass(Lglium mullzflorum) decahydroqumolme 40 Italian millet (Setariailalica) E 1 11' 6 l-(2-chloroethylthlo-carbonyl)- 140/0.1 Torr gi gfgrass trans-decahydroquinoline b) in Water h d P t l 7l-(2-chloroethylthio-carbonyl)-cis- 138/0.08 Torr gyg gfg grass g ig zifl decahydmqumolme crabgrass (Digilaria sanguinalis) TABLE 111 Conditionof the sown plants after 4 weeks Active Crop Plants Weeds substanceCone. Rice Rice in Cot- Lulium Setaria Echinachloa Poa Alopu- DigitariaExample kg/ha dry water wheat Soya ton Maize mulnfl. ital. crus gullirriv. cums sanguin.

No. dry in myos.

water 1 8 9 8 8 9 9 9 2 2 1 1 1 2 1 4 9 8 9 9 9 9 3 2 1 2 l 2 l 2 9 9 99 9 9 8 2 2 2 2 9 l l 9 9 9 9 9 9 9 4 2 6 9 9 2 2 8 9 7 8 7 8 8 1 1 1 11 1 1 4 9 3 8 7 9 8 2 1 1 1 1 2 1 2 9 9 9 9 9 8 7 1 2 2 1 2 1 l 9 9 9 99 9 9 2 2 2 l 7 2 3 8 8 9 9 9 3 2 l l 2 2 2 4 9 9 9 9 3 2 l 2 2 2 2 2 88 9 9 9 9 3 2 2 3 2 2 3 l 9 9 9 9 9 9 7 4 5 9 4 4 4 4 8 7 7 7 1 1 1 1 11 1 4 8 8 7 1 1 2 1 1 2 1 2 8 8 9 9 8 2 l 3 2 1 2 l 1 9 9 9 9 9 6 1 5 42 6 1 A 4 9 9 9 9 9 3 3 3 l 4 6 2 2 9 9 9 9 9 9 4 6 7 8 6 3 l 9 9 9 9 99 9 7 9 9 9 9 A= 3(cthyllhio-carhonyl)-3-uzuhicyclo[3.2.2r]nnnane, knownfrom US Patent No. 3344.134

'A mixture of grasses, consisting of Lolium perenne (20 percent), Poapratensis (23 percent), Festuca ovin percent) and Festuca rubra (47percent), is cultivated for 4 months in seed dishes and cut once weekly.The freshly cut grass, approx. 1.5 cm high, is then treated with aqueousor aqueous-acetonic active substance solutions. Subsequently the grassiskept at 25C and 65 percent relative atmospheric humidity under' 15000lux. The growth in height is assessed 4 weeks after the application ofthe active substances. Thediminuti'on produced by the active substanceat various ratesof application is indicated in the Table belowinaccordance with the following rating.

Key 6 no action, as untreated grass 5 approx. l6% inhibition of thegrowth in-height 4 approx. 35% inhibition of the growth in height 3approx. 50% inhibition of the growth in height 2 approx. 66% inhibitionof the growth in height 1 approx. 85% inhibition of the growth in heightc deeper leaf colouring 15000 lux. The diminution in the growthinheightof the plants is determined by measuring the. internodalintervals. 3 y

The growth inhibition produced by the active-substances is indicated inthe following Table in accordance with the rating as given above.

Table V V 1 Active Substance Concentration Spring Wheat "Rye OatsExample No. ppm 7 I000 5 I 3 4 H The other substances are tested inshowed a similar action. The herbicidal agents according to theinvention are manufactured in known manner by intimately mixing and/orgrinding active substances of the formula I with like manner and thesuitable carriers, optionally with the addition of dispersants orsolvents which are inert towards the active substances. The activesubstances may be available and can beused in the following forms:

Solid Forms dusts, tracking agents, granules, coated granules, im

pregnated granules and homogeneous granules.

Table III- Active' Substance Concentration Lolium. Poa Festucca FestucaExample No. v kg/ha perenne pralznsis rubra ovin l l0 5 3c 6 6 5 5 6 6 62 l0 4 le 4 3c 5 5 2c 5 3c 3 l0 5 4c 5 4 5 6 4c 5 4 4 l0 2 3c 4 3 5 4 3c4 4 b. Application to cereals Liquid Forms Spring wheat, rye and oatsare cultivated in seed dishes at 25C, 65 percent relative atmospherichumidity and 15000 lux. When the plants have attained the 2 leaf stagethe seed dishes are treated with an active substancef'broth, so that theindicated rate of application is achieved. The growth in length isassessed 21 days after application in accordance with the key in a)above.

The same types of cereal, spring wheat, rye and oats, in the 2 leafstage are sprayed dripping wet with aqueous or aqueous acetonicsolutions of 0.5 percent active substance and then kept in a climaticchamber at 25C and 65 percent relative atmospheric humidity under a.active substances which are dispersible in water:

wettable powders, pastes, emulsions; b. solutions.

To manufacture solid forms (dusts, tracking agents),

the active substances are mixed with solid carriers.

Suitable carriers are, for example: kaolin, talcum, bolus, loess, chalk,limestone, ground limestone, attaclay, dolomite, diatomaceous earth,precipitated silica, alkaline earth silicates, sodium and potassiumaluminium silicates (feldspar and mica), calcium and magnesiumsulphates, magnesium oxide, ground synthetic materials, fertilisers, forexample ammonium sulphate, ammonium phosphate, ammonium nitrate, urea,ground vegetable products, such as corn meal, bark dust, sawdust,nutshell meal, cellulose powder, residues of plant extractions,activated charcoal etc. These substances can either be used alone or inadmixture with one another.

The particle size of the carriers for dusts is advantageously up toabout 0.1 mm, for tracking agents about 0.075 to 0.2 mm, and forgranules 0.2 mm or larger.

The concentrations of active substance in the solid preparations areusually from 0.5 to 80 percent.

To these mixtures can also be added additives which stabilize the activesubstance and/or non-ionic, anionic and cationic surface activesubstances, which for example improve the adhesion of the activeingredients on plants or parts of plants (adhesives and agglutinants)and/r ensure a better wettability (wetting agents) and dispersibility(dispersing agents). Examples of suitable adhesives are the following:olein/chalk mixture, cellulose derivatives (methyl cellulose,carboxymethyl cellulose), hydroxyethyl glycol ethers of monoalkyl anddialkyl phenols having to ethylene oxide radicals per molecule and 8 to9 carbon atoms in the alkyl radical, lignin sulfonic acids, their alkalimetal and alkaline earth metal salts, polyethylene glycol ethers(carbowaxes), fatty alcohol polyethylene glycol ethers having 5 toethylene oxide radicals per molecule and 8 to 18 carbon atoms in thefatty alcohol moiety, condensation products of ethylene oxide/propyleneoxide, polyvinyl pyrrolidones, polyvinyl alcohols, condensation productsof urea and formaldehyde, and also latex products.

The water-dispersible concentrates of the active substance, i.e.wettable powders, pastes and emulsifiable concentrates, are agents whichcan be diluted with water to any concentration desired. They consist ofactive substance, carrier, optionally additives which stabi lize theactive substance, surface-active substances and anti-foam agents and,optionally, solvents.

Wettable powders and pastes are obtained by mixing and grinding theactive substances with dispersing agents and pulverulent carriers insuitable apparatus until homogeneity is attained. Carriers are, forexample, those mentioned for the solid forms of application. In somecases it is advantageous to use mixtures of different carriers. Asdispersing agents there can be used, for example, condensation productsof sulfonated naphthalene and sulfonated naphthalene derivatives withformaldehyde, condensation products of naphthalene or naphthalenesulfonic acids with phenol and formaldehyde, as well as alkali, ammoniumand alkaline earth metal salts of lignin sulfonic acid, in addition,alkylaryl sulfonates, alkali and alkaline earth metal salts of dibutylnaphthalene sulfonic acid, fatty alcohol sulfates such as salts ofsulfated hexadecanols, heptadecanols, octadecanols, and salts ofsulfated fatty alcohol glycol ethers, the sodium salt of oleoylethionate, the sodium salt of oleoyl methyl tauride, ditertiaryacetylene glycols, dialkyl dilauryl ammonium chloride and fatty acidalkali and alkaline earth metal salts.

Suitable anti-foam agents are silicones.

The active substances are so mixed, ground, sieved and strained with theadditives mentioned above that, in wettable powders, the solid particlesize of from 0.02 to 0.04 and in pastes, of 0.03 is not exceeded. Toproduce emulsifiable concentrates and pastes, dispersing agents such asthose given in the previous paragraphs, organic solvents and water areused. Examples of suitable solvents are the following: alcohols,benzene, xylenes, toluene, dimethyl sulfoxide, and mineral oil fractionsboiling between 120 and 350C. The solvents must be practically odorless,not phytotoxic, inert to the active substances and not readilyinflammable.

Furthermore, the agents according to the invention can be applied in theform of solutions. For this purpose the active substance or severalactive substances of general formula l are dissolved in suitable organicsolvents, mixtures of solvents or in water. Aliphatic and aromatichydrocarbons, chlorinated derivatives thereof, alkyl naphthalenes, andmineral oils alone or mixed with each other, can be used as organicsolvents. The solutions should contain the active substances in aconcentration of from 1 to 20 percent.

The agents described according to the invention may be mixed with otherbiocidally active compounds or agents. Thus to broaden the activityspectrum the new agents may contain, for example, insecticides,fungicides, bactericides, fungistatics, bacteriostatics or nematocides,in addition to the cited compounds of the formula I.

Preparations forms of the new substituted azabicycloalkanes aredescribed hereinbelow. Parts denote parts by weight.

Granules The following substances are used to manufacture 5 percentgranules:

5 parts of an active substance of the formula l,

0.25 parts of epichlorohydrin,

0.25 parts of cetyl polyglycol ether,

3.50 parts of polyethylene glycol ether (Carbowax),

91 parts of kaolin (particle size: 0.3-0.8 mm).

The active substance is mixed with epichlorohydrin and the mixturedissolved in 6 parts of acetone, then polyethylene glycol ether andcetyl polyglycol ether are added. The resulting solution is sprayed onkaolin and then evaporated in vacuo.

Wettable Powder The following constituents are used to manufacture (a) apercent, (b) a 25 percent and (c) a 10 percent wettable powder:

a. 70 parts of an active substance of the formula I,

5 parts of sodium dibutylnaphthalene sulphonate, 3 parts ofnapthalenesulphonic acid/- phenolsulphonic acid/formaldehyde condensate(3:2:1), 10 parts of kaolin, 12 parts of Champagne chalk;

b. 25 parts of an active substance of the formula I, 5 parts of sodiumoleylmethyltauride, 2.5 parts of naphthalenesulphonic acid/formaldehydecondensate, 0.5 parts of carboxymethyl cellulose, 5 parts of neutralpotassium aluminium silicate, 62 parts of kaolin;

c. 10 parts of an active substance of the formula 1,

3 parts of a mixture of the sodium salts of saturated fatty alcoholsulphates, 5 parts of naphthalenesulphonic acid/formaldehyde condensate,82 parts of kaolin.

The indicated active substance is applied to the cor responding carriers(kaolin and chalk) and then these are mixed and ground, to yieldwettable powders of excellent wettability and having an excellentcapacity for forming suspensions. By diluting these wettable powderswith water it is possible to obtain suspensions of every desiredconcentration of active substance. Such suspensions are used forcombating weeds and weed like grasses in cultures of water and dry ricebefore and after the emergence of the rice plants.

Paste The following substances are used to manufacture a 45 percentpaste:

45 parts 1.,of v1-(3 chloropropylthio-carbonyl)-cisdecahydroquinoline,'5parts of sodium aluminium sili cate,. l4 parts of cetylpolyglycolether'with 8 mols' of ethylene oxide, 1 parts of oleylrpolyglycol etherwith mols of ethylene oxide, 2 parts of spindle oil, 10 parts ofpolyethylene glycol, '23 parts of water.

The active substanc is intimately mixed with the additives inappropriate devices and ground. A paste is obtained from which, bydiluting it with water, it is possible to manufacture suspensions ofevery desired concentration of active substance. The suspensions aresuitablefortreating cultures of water rice before and after theemergence of the plants.

Similar pastes are obtained if another active. substance .of. theformula I is used instead of the above m' ntibn id? decali ydroquinoline.

Emulsion Concentrate To manufacture a 10% emulsion concentrate 10 partsof decahydroquinoline, parts of oleyl polyglycol ether with.8 mols ofethylene oxide, 75 parts of isophoron are mixed together. Thisconcentrate can be dilutedwith water to give emulsions in desiredconcentrations. Such emulsions are applied, for example, to cultures ofdry rice before the emergence of the rice plants.

l-(allylthio-carbonyl)-transdecahydroquinoline or l-(3-chloropropylthio-carbonyl )-cis- Similar emulsion concentrates areobtained if, for example, l-(allylthio-carbonyl)-2-methyl- 1-(3-chloro-propylthio-carbonyl)-octahydroindole is used instead of theabove mentioned active substance.

We claim:

l. A compound of the formula 'wh erein R is chloroalkyl having or 3carbon'atomst

1. A COMPOUND OFTHE FORMULA
 2. The compound according to claim 1 whichis 1-(3-n-chloropropylthio-carbonyl)-2-methyloctahydroindole.